Oil acid-modified polyhydric alcohol-polybasic acid resin



Patented June 16 1942 OIL ACID- MODIFIED POLYHYDRIC ALCOHOL-POLYBASICACID RESIN Edwin T. Clocker, Bethlehem, Pa.

No Drawing. Application May 4, 1939, Serial N0. 271,719

14 Claims.

improved condensation product by causing condensation between an alkylmono-substituted or alkyl di-substituted olefinic acid having less thanten carbon atoms in the carbon chain and a compound of the groupconsisting of nonconjugated unsaturated nonhydroxylated aliphatic acidshaving from ten to twenty-four carbon atoms in the carbon chains; saltsthereof; esters thereof or similar compounds. As explained below anyrelatively short chain compound containing the ethylene linkage incondensable form may be condensed with any nonconjugated unsaturatednonhydroxylated aliphatic acid or the like having from ten totwenty-four carbon atoms.

in its carbon chain.

A further purpose is to cause a condensable ethylene type compoundhaving less than ten carbon atoms in its carbon chain to attach to thecarbon chain of a nonconjugated unsaturated nonhydroxylated fatty acidor the like by suit-,

able application of heat and, desirably also, pressure. A temperature ofbetween 150C. and 300 C. is preferred for the reaction, 180 C. to 260 C.

being the most satisfactory range. A temperature in excess of 150 C. isdesirably maintained for a time of at least three-quarters of an hourand suflicient to produce substantial condensation. Good results areobtained using a temperature not less than 150 C. and in excess of theordinary boiling point of .the condensable ethylene type compound withreturn condensation.

A further purpose is to cause one molecular equivalent of a condensableethylene type compound having less than ten carbon atoms in its carbonchain to condense with one molecular equivalent of a nonconjugatedunsaturated nonhydroxylated carbon chain compound having from ten totwenty-four carbon atoms in the carbon chain.

A further purpose is to partially or completely saturate the doublebonds of a nonconjugated unsaturated nonhydroxylated fatty acid, fattyoil or the like by an alkyl monoor di-substituted olefinic acid havingless than ten carbon atoms in the carbon chain A further purpose is tocondense maleic anhydride 'or the like with a drying oil such as linseedoil, and to cause the condensation product to dry in air at ordinarytemperatures or at elevated temperatures, either in the presence of adrier or without a drier.

A further purpose is to produce my novel condensation product in a formwhich has a polarreactive group. e

A further purpose is to cause the acid or acid anhydride group of acondensation product of an alkyl-substituted olefinic acid or acidanhydride having less than ten carbon atoms in its carbon chain with anonconjugated unsaturated nonhydroxylated fatty acid or the like havingfrom ten to twenty-four carbon atoms in its carbon chain to react withother compounds such as metal salts or metals. A further purpose is toproduce an improved varnish or the like from the condensation product ofan olefinic acid having less than ten carbon atoms in its carbon chainand a nonconjugated unsaturated nonhydroxylated drying oil, by theaddition of an alcohol which will combine with the acid group and alsoof av resin, suitably heating the ingredients to varnish viscosity andthinning with a suitable solvent.

Further purposes appear in the specification and in the claims.

It has been known for some time that maleic anhydride or substancesyielding maleic anhydride will condense with carbon chain compoundscontaining a conjugated system of double bonds. For example, Morrell,Marks and Samuels in British Patent No. 407,957 discloses a condensationof maleic anhydride with tung oil, a conjugated compound.

I have discovered that, under suitable conditions, maleic anhydride andcompounds which behave similarly, as discussed below, will react withnonconjugated unsaturated nonhydroxylated fatty oils and acids andsimilar compounds having from ten to twenty-four carbon atoms in thecarbon chain to produce a wide variety of products depending upon thecharacters of the reacting substances and the subsequent reactions towhich the condensation products are subjected.

The maleic grouping must be present in condensable form, preferably asmaleic anhydride. The condensation is of course obtained from any of thecompounds which yield maleic anhydride, such as malic acid, fumaricacidor maleic acid. The production of maleic anhydride from such other acidsis well known in the art (Be'rnthsen, Textbook of Organic Chemistry(1923) pages 250456). Instead of maleic anhydride, an ester of maleicacid, whether an acid or completed ester, may be used; also asubstituted maleic acid.

Investigation of a large number of compounds has shown that condensationwith a noncon- Jugated unsaturated nonhydroxylated aliphatic acid havingfrom ten to twenty-four carbon atoms in the carbon chain is generallycharacteristic of chain compounds having the ethylene linkage and havingless than ten carbon atoms in the carbon chains, which are substitutedon.

one or both sides of the double bond to form acids or acid anhydrides,or similar compounds. These compounds are olefinic as they are acyclicand have the ethylene linkage. Such olefinic compounds aremono-substituted when they contain only one acid, acid anhydride oresterified group; for example crotonic acid. Such olefinic compounds aredi-substituted when they contain two acid, acid anhydride or esterifiedgroups; for example maleic anhydride, citraconic anhydride, maleic acid,acid methyl maleate. v

When I refer to the olefinic compound of less than ten carbon atoms inthe carbon chain as having the ethylene linkage in condensable form, Imean to indicate that the compound is not a hydrocarbon, for example,but that it is an acid or acid anhydride or an ester or half esterthereof or a similar compoundv which will condense with a nonconjugatedunsaturated nonhydroxylated fatty acid or the like having from ten totwenty-four carbon atoms in the carbon chain.

The longer the carbon chain of the substituted olefinic acid or acidanhydride, or ester or half ester thereof, or similar compound, the lessvigorous is the condensation reaction. Thus at the upper limit (ninecarbon atoms in the carbon chain) the reaction "is relatively mild. Ifthere are less than seven carbon atoms in the carbon chain (for examplesix) the reaction is more vigorous. A still more vigorous reaction isobtained if there. are less than five carbon atoms in the carbon chain.

In all cases where I refer in the specification to less than ten carbonatoms in the carbon chain of the substituted olefinic compound, it willbe understood that a more vigorous reaction is obtained with compoundshaving less than seven carbon atoms in the carbon chain, and a stillmore vigorous reaction with compounds having less than five carbon atomsin the carbon chain. These latter groups (less than seven and less thanfive) are to be taken as expressly included, although not specificallymentioned because of a desire to shorten the specification.

When reference is made to the maleic grouping in condensable form, itwill be understood that it is intended to designate maleic anhydride, asubstance yielding maleic anhydride or a maleic es ter or similarcompound which is capable of condensing to enter the carbon chain of anonconjugated unsaturated nonhydroxylated aliphatic compound having fromten to twenty-four carbon atoms in the carbon chain. A maleiccondensation product may be obtained from any such compound having themaleic grouping, preferably maleic anhydride.

As will be later explained in considerable detail, the presence oft'neacid or acid anhydride radical in the condensation product isdistinctly advantageous, because of the reactions of which the acid oracid anhydride radical is capable and the uses to which such reactionsmay-be put.

A wide variety of nonconjugated unsaturated nonhydroxylated carbon chaincompounds having from ten totwenty-four carbon atoms in the carbon chainmay be employed. Esters of fatty acids with mono-, dior poly-hyd'ricalcohols,

for example glyceryl or glycol esters, are par- I pounds having tencarbon atoms, twenty-four carbon atoms or any intermediate number ofcarbon atoms in the chain. The reference to the length of the carbonchain applies to the carbon chain of the acid. A glyceride, for example,contains three such carbon chains united to a glyceryl group.

As examples of the type of nonconjugated unsaturated nonhydroxylated'aliphatic acids having from ten to twenty-four carbon atoms in thecarbon chain which I may use, I suggest oleic, linolic, linolenic,clupanodonic and undecylenic. The esters of the nonhydroxylated fattyacids may be either glyceryl esters, which form oils such as corn, olive(triolein), cotton seed, peanut, linseed, sunflower, satllower, perilla,hemp seed, walnut seed, soya, rape seed, tomato seed, neats foot, lard,codliver; burbet, salmon, cod, menhaden, and many others, all noncon-J'ugated unsaturated nonhydroxylated fatty oils; or esters of otheralcohols, for example glycol esters. It will furthermore be understoodthat mixtures of various esters, or 'of the esters and the free fattyacids, or of salts of the acids, may be employed if desired.

When I refer to the grouping of a nonconjugated unsaturatednonhydroxylated aliphatic acid having from ten to twenty-four carbonatoms in the carbon chain, I mean to include the acid, and compounds ofthe acid such as esters of the acid, whether with mono-, diorpolyhydric-alcohols, and salts of the acid. I,do not include hereinhydroxylated aliphatic acids, oils, etc., because, while thecondensation of my invention may in certain cases be obtained with them,special precautions must be taken because of the tende lf y 0fhydroxylated fatty acids, oils, etc., to esterify and gel. A typicalhydroxylated fatty oil is castor oil. The question of whether the freeacid or the ester or the salt is used is immaterial from the standpointof the condensation reaction because the condensation reaction with thealkyl substituted olefinic compound having less than ten carbon atoms inits carbon chain appears to involve the carbon chain at an intermediatepoint between its ends, rather than the carboxyl group or neutralizedcarboxyl group at the end of the chain. Of course, the character of theproduct will vary depending upon whether the acid, ester or salt isused.

- In the condensation, I may desirably employ one molecular equivalentof nonconjugated unsaturated nonhydroxylated acid or the like to onemolecular equivalent of alkyl substituted olefinic compound and subjectthe mixture to a temperature of between C. and 300 C. and preferablyalso to high pressure to facilitate the reaction. Pressure may desirablybe applied by simply confining the reaction components between the wallsof some vessel such as a pressure autoclave and then heating thereaction components. Pressure may also be applied in any other suitableway, as by pumping the reacting components into the vessel orintroducing.

an inertgas under pressure. I have used pressures up to 300 pounds persquare inch with suceess. Of course the desirable pressure will varywith the individual reaction. I

A suitable catalyst may be used'to accelerate the reaction and toincrease the yield. I do not, however, find that. acatalyst isnecessary.

The condensation reaction may be carried out in the presence of suitablesolvents, although this is not usually necessary.

In ordinary practice I prefer not to use sufficient alkyl substitutedolefinic compound having less than ten carbon atoms in the carbon chainto saturate all of the double bonds in the fatty acid or fatty oil,-etc., having from ten to twenty-four carbon atoms in the carbon chain.The condensation product thus ordinarily has an iodine value. saturateone-sixth to one-third of the double bonds in the fatty acid, fatty oil,etc. Thus in olive oil one-third of the double bonds (one) is ordinarilysaturated. and in linseed oil one-sixth (one). But in individual casesit may be desirable to satisfy more ethylene linkages in the fatty acidor fatty oil, and even to completely saturate them. To saturate all ofthe ethylene linkages in linseed oil, six molecular equivalents Example1 Generally it is sufilcient to In a pressure autoclave, 180 parts byweight of linseed oil are mixed with 20 parts by weight of maleicanhydride (an alkyl di substituted olefinic acid anhydride) Thetemperature is maintained at from 250 C. to 260 C. for one hour. Thereaction may be obtained satisfactorily at 150 C., but is much slower atthis low temperature, and the temperature may be raised to as much as,300 C., but a high temperature may cause some difficulty due tocarbonization. After cooling the reaction product is removed from theautoclave. The condensation product is slightly darker and more viscousthan the original linseed oil. It is soluble in acetone, ethyl acetate,ether, xylene, carbon tetrachloride, higher petroleum hydrocarbons andturpentine; and semi-soluble in 95% ethyl alcohol. The condensationproduct is miscible with fatty oils and solutions of nitrocellulose inall proportions. The iodine value is 141.4. as against 190.0. for theoriginal linseed oil. The saponification value is 288 and the acid valueis 52.9., in the presence of ethyl alcohol.

Example 2 Into a three-neck fiask,'equipped with a thermometer,mechanical stirrer and condenser, 200 parts by weight of distilled oleicacid and 60 parts b weight of maleic anhydride are placed and heat isapplied until the temperature of the mixture reaches 180 C., at whichpoint the maleic anhydride boils.

The temperature is gradually raised from 130 C. to 250 C. over a periodof one hour, during which time the amount of condensed maleic anhydrideprogressively diminishes. The temperature is maintained at 250 C. to 260C. until no more maleic anhydride appears to condense. The temperaturesgiven are those found best for carrying out the reaction, although.temperatures between C. and 300 C. may be used.

The condensation product is soluble in ethyl alcohol, ether, xylene,carbon tetrachloride and solutions of nitrocellulose, but issubstantially insoluble in petroleum hydrocarbons and fatty oils.

Example 3 To 180 parts by weight of linseed oil are added 25 parts byweight of citraconic anhydride (an alkyl di-substituted olefinic acidanhydride) and the 'mixture is heated in a three-neck flask, equippedwith a reflux condenser, at about 250 C. for about three-quarters of anhour. At the end of this period, no further citraconic anhydride appearsto condense, indicating completion of the reaction. As a precaution,heating is continued for about 15 minutes longer. The reaction productis less viscous than the maleic condensation product of linseed oilobtained in Example 1, but has the same properties otherwise.

Example 4 The condensation product has similar properties to themaleic-linseed oil condensation product obtained in Example 1 asrespects solubility above noted, and dispersing power, drying action andadherence to metals, noted below.

My novel condensation product may be made with nonconjugated unsaturatednonhydroxylated drying, semi-drying or nondrying fatty oils havingfrom-ten to twenty-four carbon atoms in the carbon chain, or mixtures ofthe same, and the characteristics of the product are, to some extent,dependent upon the character of the oils or the like employed in thereaction. When nonconjugated unsaturated nonhydroxylated drying oils arecaused to react with alkyl-substituted olefinic acids or acid anhydrideshaving less than ten carbon atoms in the carbon chains, the products dryin the air at ordinary temperatures to form hard dry films whether ornot driers are used. Likewise, the condensation products ofnonconjugated unsaturated nonhydroxylated drying oils generally exhibitthermohardening properties, being convertible at 70 C. to 80., forexample into hard resistant varnish-like films in short periods of time,An example of the drying behavior of the condensation product obtainedby Example 1 is as follows:

Example 5 A 1:1 xylene'solution of the reaction product obtained inExample 1 to which soluble driers are added to the extent of 0.03% ofcobalt, 0.05% of manganese and 0.5% of lead, for example in the form oflinoleates or resinates, dries to a hard film at room temperature inabout five hours and may be stoved to a hard film at 80 C. in about oneand one-half hours. The film produced is not acted upon by water, ethylalcohol, benzene, or xylene,

It is thus evident that the invention permits of the direct productionof thermo-hardening and air-drying lacquers, varnishes, etc.

Without limiting myself to any exact structure for the condensationproduct, it would appear that the condensation product is an additionproduct at a double bond in the carbon chain of the nonconjugatedunsaturated nonhydroxylated fatty acid or the like to the condensablealkyl substituted olefinic compound or the like.

For example, if linolenic. acid reacts with maleic anhydrlde, the firststage in the reaction appears to be in general as follows. Of course ifenough maleic anhydride be present, the same reaction will take place ateach double bond in the linolenic acid.

CHQCHQCHICHCIDCH=CHCH2CII=CH(CH2)7COOH-{- linolcnic acid HC=CH heat O OO maleic anhydride CHaCH2CH-CHCH2CH=CHCH2CH=CH(CH2)7COOH maleiccondensation product of linolenic acid The iodine value of thecondensation product confirms the above formula, and indicates that theethylene linkage of the olefinic compound (in this case maleicanhydride) has been lost during condensation. It should be noted thatone of the double bonds in linolenicacid and the ethylene linkage inmaleic anhydride appear to have disappeared in the condensation productforming a ring type compound with four carbon atoms in the ring.

The condensation product appears to be char acterized by the linkage:

x g- L-YCOZ where VCCW is a grouping of less than ten carbon atoms, Xand Y are carbon chains without conjugated double bonds and Z is ahydrogen atom, a metal or an ester group.

The reaction above will be modified in wellknown manner if a glycerylester of linolenic acidinstead of linolenic acid be used, or if someother nonconjugated unsaturated nonhydroxylated aliphatic acid havingfrom ten to twentyfour carbon atoms in the carbon chain be employed, orif some other olefinic acid or acid anhydride having less than tencarbon atoms in its carbon chain be used instead of or in mixture withmaleic anhydride.

It should be noted that the alkyl-substituted olefinic acid or acidanhydride condensation product of linolenic acid or any similar acid hasi Acid or acid anhydrz'de reactions As noted above, an acid or acidanhydride group of the condensation product is capable of a wide varietyof reactions to produce desirable products of various kinds. Forexample, very satisfactory oil-soluble driers may be manufactured bycausing the condensation product oi an alkyl-substituted olefinic acidor acid anhydride having less than ten carbon atoms in the carbon chainand a nonconjugated unsaturated nonhydroxylated aliphatic. acid or thelike having from ten to twenty-four carbon atoms in the carbon chain,particularly a glyceride of such acid, to react with a metallic oxide,hydroxide, carbonate or other similar compound capable. of combinationwith the acid or acid anhydride group of the alkyl-substituted olefinicacid or acid anhydride condensation product. For example, the oxides,hydroxides and carbonates and acetates in the presence of water, andmany other salts of lead, cobalt or manganese can be caused to reactwith the maleic condensation product of linseed oil as described inExample 1, to form driers which are readily soluble in linseed oil andvery useful in the paint, varnish and lacquer industry.

A desirable feature of my invention is that the condensation product ofalkyl-substituted olefinic acids and acid anhydrides having less thanten carbon atoms in the carbon chain, with nonconjugated unsaturatednonhydroxylated drying oils forms an excellent vehicle or ingredient fora vehicle for paints, etc. This reacts with metallic oxides andhydroxides, and with carbonates and acetates in the presence of water,to form a drier which is chemically combined with the vehicle. Such adrier is made by adding a small percentage of lead oxide to the maleicanhydride condensation product of linseed oil (for example, enough tointroduce of lead into thecondensation product).

Esterification of the acid or acid anhydride group is frequentlydesirable. The alcohol used may be either aliphatic or aromatic andeither mono-, dior poly hydric. Of course, the carbon atoms in the groupadded by esterification are not counted as part of the carbon chain ofthe acid or acid anhydride used in making the 1 condensation product.

The esterified condensation product in which the maleic grouping orsimilar grouping has combined with the grouping of a nonconjugatedunsaturated nonhydroxylatedfatty drying oil exhibits the same desirableair-drying and thermohardening properties as the unesterifiedcondensation product, and may be used for paint, varnish and lacquerwork with success.

Example 6 A typical case of esterification is exhibited when 25 parts byweight of the viscous oil obtained by the interaction of maleicanhydride and linseed oil, as described for instance in Example l, aremixed with 1.6 parts by weight of ethylene glycol and the mixture ismaintained at about 180 C. until the reaction ceases. A 1:1 xylenesolution of the reaction product, when treated with a suitable quantityof metallic driers, as described for instance in Example 5, dries atroom temperature to a hard film in a somewhat shorter time than thatrequired for linseed oil and, when stoved at 80 C., gives a hard film inabout one and one-half hours. The film is not attacked by water, alcoholor xylene.

In the above reaction the ethylene glycol neutralizes the acid anhydrideand forms an ester.

I Of course, if the starting material were the conden'sation product oflinolenic acid instead of its glyceride, esterification takes place atthe carboxyl group as well as at the acid anhydride group, as thecondensation product is then polarreactive at two distinct parts of themolecule.

It is possible to manufacture improved varnish or the like byesterifying the condensation product of a nonconjugated unsaturatednonhydroxylated drying oil with an olefinic acid or the like having lessthan ten carbon atoms in its carbon chain. Glycerine, glycol or otherpoly-hydric alcohol may be employed in forming the ester. The reactionproduct should preferably be incorporated with a resin, such as rosin.This mixture may be heated to the required varnish viscosity and thenthinned with a common organic solvent,

Example 7 Heat together 100 parts by weight of the maleic anhydridecondensation product of linseed oil as obtained in Example 1, and 11parts by weight of glycerine at 230 C. until a drop of the reactionmixture remains clear on cold metal. Then add to the reaction mixture 60parts by Weight of wood rosin and heat at 285 C. for 45 minutes. Theproduct gives an acid number of as compared with 113 for the acid numberof the uncondensed mixture.

This product, when out with petroleum spirits containing drier, dries toa hard, water-resistant film.

The polar-reactive quality of the acid or acid anhydride in an alkylsubstituted olefinic acid or acid anhydride having less than ten carbonatoms in the carbon chain is of great importance when its condensationproduct with a nonconjugated unsaturated nonhydroxylated aliphatic acidor the like having from ten to twentyfour, carbon atoms in its carbonchain is used'as a metal coating. In this instance the acid or acidanhydride group acts upon the metal which is coated and produces verytenacious adherence of the fi m. This makes the alkyl substitutedolefinic acid or acid anhydride condensation product of a nonconjugatedunsaturated nonhydroxylated aliphatic acid or oil or the like havingfrom ten to twenty-four carbon atoms in its carbon chain very desirableas a base or priming coat. The suitability of the alkyl substitutedolefinic condensation product of a nonconjugated unsaturatednonhydroxylated acid or the like for priming or base coat purposes isincreased when nitrocellulose lacquers are employed for a subsequentcoat or coats, because nitrocellulose solutions (for example,nitrocellulose dissolved in ethyl alcohol and ethyl acetate) arecompletely miscible with the alkyl substituted olefinic condensationproduct and firm adherence between the condensation product coat and thenitrocellulose coat or coats is thus obtained.

The advantage of the condensation product as a base for nitrocelluloseis present whether the alkyl-substituted olefinic compound be an acid oracid anhydride, or whether it be an ester or half ester.

My novel condensation product is very satisfactory for use withnitrocellulose solutions in lacquers, etc. The proportions need not berestricted, although I have found that 20% to 50% of nitrocellulosesolution and 80% to 50% of condensed drying oil make a suitable vehicle.The polar-reactive groups in the condensed drying oil give firmadherence.

I believe I am the first to discover that alkylsubstituted olefinicacids and acid anhydrides having less than ten carbon atoms in'thecarbon chain, preferably less than seven carbon atoms in the. carbonchain and still better less than five carbon atoms in the carbon chain,will condense with the carbon chain of a nonconjugated unsaturatednonhydroxylated aliphatic acid, ester,

salt, etc, having from ten to twenty-four carbon atoms in the carbochain. I frequently refer to such nonconjugated unsaturated aliphaticacids, esters, salts, etc as nonconjugated unsaturated nonhydroxylatedfatty acid compounds, or compounds having the fatty acid grouping.

It is of course within the ability of any routine chemist to suggestother analogous compounds which may be used without departing from myinvention, such as neutralized alkyl-substituted olefinic half esters,etc., which are to be regarded as equivalents of the compoundsmentioned. For different compounds, some variations in desirablereaction temperatures and pressures will be Throughout the specificationand claims, where I refer to nonconjugated unsaturated nonhydroxylatedaliphatic acids having from ten to twenty-four carbon atoms in thecarbon chains, or salts or esters thereof, I mean such acids,

salts or esters as are unoxidized or nonpolymerized or not suificientlyoxidized or polymerized to interfere with the reactions disclosedherein. Thus, in referring to linseed oil, I mean the product generallyknown as such, raw or refined, and not linseed oil sufiiciently oxidizedor polymerized to prevent or seriously interfere with the formation of acondensation product at a double bond. In other words, I do not intendto exclude others from mere esterification of oxidized or polymerizedfatty oils by some acidic substance, such as maleic anhydride.

Many of the fish oils contain varying percentages of fatty alcohols,which will of course react with a substance of the type of maleicanhydride to form esters. The esterified fatty alcohols may be allowedto remainin the condensation product, or the alcohols may be removedbefore condensation takes place.

Where reference is made to poly-hydric alcohols, it is intended toinclude di-hydric alcohols.

Under the designation poly-hydric alcohols, itis intended to includesubstituted poly-hydric alcohols such as glycol monoethyl other.Reference to acids is intended to include acid anhydrides and halfesters of acids. Reference to esters is intended to include partiallycompleted esters such as half esters.

In view of my invention and disclosure .Variations and modifications tomeet individualwhim or particular need will doubtless become evident toothers skilled-in the art, to obtain all or part of the benefits of myinvention without copying the process or product disclosed, and I,therefore, claim all such in so far as they fall within the reasonablespirit and scope of my invention.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patentis:

1. The method of producing a resin from a fatty acid, a polybasic acidand a polyhydric the polyhydric alcohol.

2. The method of producing a resin from a fatty acid, a polybasic acidand a polyhydric alcohol, which comprises heating essentially maleicacid with linoleic acid at elevated temperatures in the substantialabsence of free polyhydric alcohol until the reaction between the acidshas taken place, and then adding a polyhydric alcohol to the acid massand continuing the reaction until the polyhydric alcohol has reactedwith the acid mass.

3. The method of producing a resin from a fatty acid, a polybasic acidand a polyhydric alcohol, which comprises heating essentially maleicacid with linolenic acid at elevated temperatures in the substantialabsence of free polygroups of the acids and the hydroxyl groups of freepolyhydric alcohol, continuing the heating until a substantial quantityof maleic acid has combined with the linolenic acid, and then adding apolyhydric alcohol thereto in quantity suihydric alcohol until thereaction between the acids has taken place, and then adding a polyhydricalcohol to the acid mass and continuing the reaction until thepolyhydric alcohol has reacted with the acid mass.

4. The method of producing a resin from a fatty acid, a polybasic acidand a polyhydric alcohol, which comprises. heating essentially maleicacid with a nonconjugated, unsaturated,

nonhydroxylated aliphatic acid having from ten' to twenty-four carbonatoms in the carbon chain at a temperature of at least 180 C. in thesubstantial absence of free polyhydric alcohol, continuing the heatinguntil a' substantial quantity of maleic acid has combined with the fattyacid, and then adding a polyhydric alcohol thereto in quantitysuflicient to esterify at the acidic group of the fatty acid and at theacidic groups of the maleic acid and continuing the heating until thereaction ceases.

5. The method of producing a resin from a fatty acid, a ,polybasic acidand a polyhydric alcohol, which comprises heating essentially maleicacid with linoleic acid at a temperature of at least 180 C. in thesubstantial absence of free polyhydric alcohol, continuing the heatinguntil a substantial quantity of maleicacid has combined with thelinoleic acid, and then adding a polyhydric alcohol thereto in quantitysufficient to esterify at the acidic group of the fatty acid and at theacidic groups of the maleic acid and continuing the heating until thereaction ceases.

6. The method of producing a resin from a fatty acid, a polybasic acidand a polyhydric alcohol, which comprises heating essentially maleicacid and linolenic acid at a temperature flcient to esterify at theacidic group of the fatty acid and at the acidic groupspf the maleicacid and continuing the heating until the reaction ceases.

7. A fatty acid-polybasic acid-polyhydric alcohol resin produced inaccordance with the process of claim 1.

8. A fatty acid-polybasic acid-polyhydric alcohol resin produced inaccordance with the process of claim 4.

9. A fatty acid-polybasic acid-polyhydric alco hol resin produced inaccordance with the process of claim 5.

10. The method of producing soluble, oil acidmodified polyhydricalcohol-polybasic acid resins, which comprises heating essentiallymaleic acid and the acids obtainable upon hydrolysis of linseed oil atelevated temperatures in the substantial absence 01' free polyhydricalcohol until reaction between the acids has taken place, and thenadding polyhydric alcohol to the acid mass and continuing the reactionuntil a homogeneous, soluble resin is obtained.

11. The method of producing soluble, oil acidmodified polyhydricalcohol-polybasic acid resins, which comprises heating essentiallymaleic acid and the acids of linseed oil at elevated temperatures in thesubstantial absence of free polyhydric alcohol until reaction betweenthe acids has taken place, and then adding a quantity of polyhydricalcohol suflicient to neutralize the acids and continuing the heatinguntil a homogeneous oil-soluble resin is obtained.

12. The method of producing oil soluble, oil acid-modified polyhydricalcohol-polybasic acid resins, which comprises heating essentiallymaleic acid and the free-acids of linseed oil at approximately 360 F.for at least about minutes in the substantial absence of free polyhydricalcohol, and then adding thereto a quantity of polyhydric alcoholsubstantially equivalent to the total amount of acids and continuing theheating until a homogeneous oil-soluble resin is obtained.

13. A soluble polyhydric alcohol-maleic acidlinseed oil acid resinproduced in accordance with the process of claim 10. 14. An oil-solublepolyhydric alcohol-maleic acid-linseed oil acid resin produced inaccordance with the process of claim 11.

EDWIN T. CLOCKER.

